Covalent crystalline structure

Cubic and Hexagonal Diamond. Each diamond tetrahedron combines with four other tetrahedra to form strongly-bonded, three-dimensional and entirely covalent crystalline structures. Diamond has two such structures, one with a cubic symmetry (the more common and stable) and one with a hexagonal symmetry found in nature as the mineral lonsdaleite (see Sec. 2.5). 

Ions stack together in the regular crystalline structure corresponding to lowest energy. The structure adopted depends on the radius ratio of cation and anion. Covalent character in an ionic bond itnposes a directional character on the bonding. 

The atomic and crystalline structure of the three covalent nitrides, aluminum, boron, and silicon nitrides, is less complex than that of the interstitial nitrides. Their bonding is essentially covalent. 

T ike metals minerals also exhibit typical crystalline structures. As an example, the structure of molybdenite is shown in Figure 1.17. It is hexagonal with six-pole symmetry and contains two molecules per unit cell. Each sulfur atom is equidistant from three molybdenum atoms and each molybdenum atom is surrounded by six sulfur atoms located at the comers of a trigonal prism. There are two types of bonds that can be established between the atoms which constitute the molybdenite crystal stmcture. They are the covalent bonds between sulfur and molybdenum atoms and the Van der Waals bonds between sulfur-sulfur atoms. The Van der Waals bond is considerably weaker than the covalent sulfur-molybdenum bond. This causes the bonds of sulfur-sulfur to cleave easily, imparting to molybdenite the property of being a dry lubricant. Molybdenite adheres to metallic surfaces with the development of a molecular bond and the friction between metallic surfaces is replaced by easy friction between two layers of sulfur atoms. 

The same principles that are valid for the surface of crystalline substances hold for the surface of amorphous solids. Crystals can be of the purely ionic type, e.g., NaF, or of the purely covalent type, e.g., diamond. Most substances, however, are somewhere in between these extremes [even in lithium fluoride, a slight tendency towards bond formation between cations and anions has been shown by precise determinations of the electron density distribution (/)]. Mostly, amorphous solids are found with predominantly covalent bonds. As with liquids, there is usually some close-range ordering of the atoms similar to the ordering in the corresponding crystalline structures. Obviously, this is caused by the tendency of the atoms to retain their normal electron configuration, such as the sp hybridization of silicon in silica. Here, too, transitions from crystalline to amorphous do occur. The microcrystalline forms of carbon which are structurally descended from graphite are an example. 

Two later sections (1.6.5 and 1.6.6) look at the crystalline structures of covalently bonded species. First, extended covalent arrays are investigated, such as the structure of diamond—one of the forms of elemental carbon—where each atom forms strong covalent bonds to the surrounding atoms, forming an infinite three-dimensional network of localized bonds throughout the crystal. Second, we look at molecular crystals, which are formed from small, individual, covalently-bonded molecules. These molecules are held together in the crystal by weak forces known collectively as van der Waals forces. These forces arise due to interactions between dipole moments in the molecules. Molecules that possess a permanent dipole can interact with one another (dipole-dipole interaction) and with ions (charge-dipole interaction). Molecules that do not possess a dipole also interact with each other because transient dipoles arise due to the movement of electrons, and these in turn induce dipoles in adjacent molecules. The net result is a weak attractive force known as the London dispersion force, which falls off very quickly with distance. 

The crystalline structure of diamond is best illustrated by using sticks to represent the covalent bonds. It is the molecular nature of diamond that is responsible for this material s unusual properties, such as its extreme hardness. 

Mesophases of supermolecular structure do not need a rigid mesogen in the constituent molecules. For many of these materials the cause of the liquid crystalline structure is an amphiphilic structure of the molecules. Different parts of the molecules are incompatible relative to each other and are kept in proximity only because of being linked by covalent chemical bonds. Some typical examples are certain block copolymers50 , soap micelles 51 and lipids52. The overall morphology of these substances is distinctly that of a mesophase, the constituent molecules may have, however, only little or no orientational order. The mesophase order is that of a molecular superstructure. 

An attempt was made in this paper to sketch the behavior of elemental semiconductors (with the diamond-type structure) and of the IH-V compounds (with the zinc blende strut ture) in aqueous solutions. These covalent materials, in contrast to metals, exhibit properties which sharply reflect their crystalline structure. Although they have already contributed heavily to the understanding of surfaces in general, semiconductors with their extremely high purity, crystalline perfection, and well-defined surfaces are the most promising of materials for surface studies in liquid and in gaseous ambients. 

Arsenic and Its Ores. Elementary arsenic exists in several forms. Ordinary gray arsenic is a semi-metallic substance, steel-gray in color, with density 5.73 and melting point (under pressure) 814. It sublimes rapidly at about 450"", forming gas molecules As similar in structure to P. An unstable yello v crystalline allotropic form containing AS4 molecules, and soluble in carbon disulfide, also exists. The gray form has a covalent layer structure (Fig. 11-8). 

Current methods take root in the early 1960s, when the conformational analysis of macromolecules became of general interest [29-30]. Anderson et al. [31] used model building and X-ray diffraction studies to determine the double helical structures of polysaccharides using crystalline structure data as an initial set of coordinates followed by computational sampling of new structures by rotation around selected covalent bonds. The details of these so-called hard-sphere calculations are described in Rees and Skerrett [32] and Rees and Smith [33]. This approach was also applied to carbohydrate conformations in the analysis of bacteria and polysaccharidic structures and linkages [34-35]. 

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